碳纳米材料磁性载体技术的固相吸附萃取研究

Sample pretreatment is mainly to achieve the purpose of separation, purification and enrichment for target analytes, as well as reduce the interference of impurities so as to assist the sample analysis. The key point in current analytical chemistry field is to develop sample pretreatment method and materials with the advantages of rapidity, simplicity, accuracy, high selectivity and environmental benignity. The project is schemed to combine the carbon nanomaterials possessing good adsorptivity with magnetic carrier technology having the characteristic of rapid separation, then further to study the innovative solid phase extraction technology and selective adsorption mechanism. First, more than six kinds of superparamagnetic carbon nanomaterials are prepared, and then elaborately characterized in shape, structure and performance. Second, the novel technology based on solid phase adsorptive extraction in separation and analytical field is established, furthermore, the selectivity and specificity of the composites are evaluated by selecting different types of compounds as model analytes and choosing adsorptive materials with special adsorptivity as reference materials. Third, the adsorption dynamics and adsorption isotherm of the composites are studied to explain the characteristics in adsorption process, as well as to describe the interactions between analytes and adsorbents. Finally, the guidance of carbon nanomateials with superparamagnetic carrier for analytes are found to realize the directional application for target analytes in analytical field.

样品前处理主要是实现分析物分离、纯化、富集的目的，减少其它物质或杂质等的干扰，便于后续分析。开发快速、简便、准确、选择性高和环境友好的样品前处理材料与技术已成为现代分析化学领域亟待解决的关键问题。本项目拟将具有良好吸附能力的碳纳米材料与磁性载体技术结合，开展高效吸附与快速分离一体化固相吸附萃取创新技术及其选择性吸附机理研究。首先，制备6种以上超顺磁性载体碳纳米材料，对其形态、结构和性能进行详细表征；其次，建立固相吸附萃取分离分析新技术，选择不同类型的分析物，并以具有专一吸附能力的吸附剂为阳性对照，对所制备复合材料的吸附选择性和专属性进行评价，从而阐述其吸附选择性机理；有针对性地对复合材料的吸附动力学和吸附等温线进行研究，剖析吸附过程的特征，并描述分析物与吸附剂之间的相互作用关系；最终，为所制备的超顺磁性载体碳纳米材料制定具有导向性的分析物选择准则，实现其在分析领域的目标性固相萃取广泛应用。

本基金资助项目以碳纳米材料高效吸附与磁性载体快速分离一体化固相吸附萃取的创新理念，首先开展了四氧化三铁(Fe3O4)超顺磁性纳米粒子的制备，并构建了十六烷基三甲基溴化铵(CTAB)包覆Fe3O4的混合半胶束(Fe3O4/CTAB)和Fe3O4回收壳聚糖(Fe3O4/Chitosan)的吸附萃取新模式；开展了超顺磁性羟基碳纳米管 (Fe3O4-MWCNTs-OH)、羧基碳纳米管(Fe3O4-MWCNTs-COOH)、氨基碳纳米管(Fe3O4-MWCNTs-NH2)、石墨烯(G-MNPs)、β-环糊精功能化还原氧化石墨烯(Fe3O4/RGO@β-CD)和聚乙烯亚胺-还原氧化石墨烯(Fe3O4@PEI-RGO) 等6种磁性纳米吸附材料，并成功构建了6种固相吸附萃取新技术；开展了磁性羟基或羧基碳纳米管粘合金属有机骨架化合物(MOFs)的复合纳米新材料Fe3O4-MWCNTs-OH@poly-ZIF67和Fe3O4-MWCNTs-COOH/ZIF-Eu，及新设计合成的空心碳球(HCSs)增强的磁性羧基碳纳米管复合材料HCSs@Fe3O4-MWCNTs-COOH等，并构建了4种纳米复合物的固相吸附萃取新技术。其次，开展了10种磁性碳纳米吸附材料的扫描电镜、X-射线粉末衍射和红外光谱等技术详细的特征与性能表征；最后，开展了新型磁性固相萃取技术(MSPE)结合高效液相色谱(HPLC)技术的番茄激素残留、大米除草剂、面粉黄曲霉毒素等分析新方法。本基金部分资助，制备了10种超顺磁性碳纳米吸附富集新材料，构建了10多种复杂体系固相萃取新技术，建立了10多种色谱分析新方法。发表SCI收录论文50篇、会议论文12篇，授权专利5件，获甘肃省自然科学二等奖1项，培养博士研究生10名，参加学术会议14次，完善和发展了西部分析化学科研团队。总之，完成了项目计划任务，取得了重要科研成果，实现了项目主要目标。